Colloids and Surfaces A: Physicochem. Eng.

Aspects 414 (2012) 220–227

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
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Removal of uranium(VI) from aqueous solutions by magnetic Mg–Al layered

double hydroxide intercalated with citrate: Kinetic and thermodynamic
investigation
Xiaofei Zhang a , Lanyang Ji b , Jun Wang a,c,∗ , Rumin Li a , Qi Liu a , Milin Zhang a , Lianhe Liu c
a
Key Laboratory of Superlight Material and Surface Technology, Ministry of Education, Harbin Engineering University, Harbin 150001, China
b
Hygienic Inspection and Monitor Station for Cereals and Oil of Heilongjiang Province, 150001, China
c
Institute of Advanced Marine Materials, Harbin Engineering University, 150001, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 We prepared magnetic citrate·Mg–Al

LDH via ion-exchange technique.
 It can effectively removal ura-
nium(VI) from aqueous solutions.
 Adsorption product is easily sepa-
rated by the external magnetic field.
 The maximum adsorption capacity
toward uranium(VI) is 180.00 mg g−1
at 25 ◦ C.

a r t i c l e i n f o a b s t r a c t

Article history: Magnetic Mg–Al layered double hydroxide was modified with citrate acid using a ion-exchange
Received 1 June 2012 technique. It showed higher adsorption capacity for the uranium(VI) ions compared with magnetic
Received in revised form 2 August 2012 Mg–Al layered double hydroxide without intercalating with citrate. This increasing capacity was
Accepted 5 August 2012
mainly attributable to the formation of the citrate–metal complexes in the interlayer of the magnetic
Available online 27 August 2012
citrate·Mg–Al layered double hydroxide. Batch experiments were conducted to study the effects of pH,
adsorbent dose, shaking time, and temperature on uranium sorption efficiency. The results reveal that
Keywords:
the maximum adsorption capacity is 180.00 mg g−1 when the initial uranium(VI) concentration is kept
Uranium
Magnetic Mg–Al layered double hydroxide
as 200 mg L−1 at 25 ◦ C, displaying a high efficiency for the removal of uranium(VI) from aqueous solution.
Citrate The sorption follows Freundlich model and pseudo-second-order kinetics. The thermodynamic param-
Adsorption eters such as H◦ , S◦ and G◦ show that the process is endothermic and spontaneous. In addition,
Kinetics the composite can be easily separated from the solution by a magnet after the adsorption process. This
Thermodynamics work provides an efficient, fast and convenient approach for the removal of uranium(VI) from aqueous
solutions.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction biological toxicity. Therefore, it is very important to choose

Uranium is one of the most dangerous heavy metals in the
environment because of its long half-life, high radioactivity and
∗ Corresponding author at: Key Laboratory of Superlight Material and Surface
Technology, Ministry of Education, Harbin Engineering University, Harbin 150001,
China. Tel.: +86 451 8253 3026; fax: +86 451 8253 3026.
E-mail address: zhqw1888@sohu.com (J. Wang).
a suitable and effective method to removal of uranium from
water. So far, several methods, such as chemical precipitation,
membrane separation, microbial removal, solvent extraction,
electrodialysis, and adsorption [1–8], have been extensively
applied for the removal of uranium(VI) from aqueous solutions.
Among these methods, adsorption appears to be one of the
most effective methods owning to its cost-effective, versatile
and simple features to operate for removing trace levels of ions
[9,10].

0927-7757/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2012.08.031
 X. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 220–227 221

Different types of adsorbents have been developed and tested

for removal of uranium(VI) from aqueous media [11–13]. Layered Fe3O4
double hydroxides (LDHs), because of their structure and high
anionic exchange capacity, have received considerable attention (b)

Intensity (a. u.)

311
in recent years. They have many potential applications such as sor-
bents, catalyst and catalyst supports [14–16]. Martinez-Gallegos
et al. [17] have used thermally treated hydrotalcite to immobilize
the CrO4 2− from aqueous solutions and understood the structural
effects of ␥-irradiation. Kulyukhin et al. [18] have synthesized of

440
220

400

511
Mg, Al and Mg, Nd layered double hydroxides for removal of ura-

422
111

nium from aqueous solutions. Just like LDH can be used as sorbents
and sorbents supports, it will be also used as catalyst and catalyst
supports. Vijaikumar et al. [19] have immobilized L-proline onto the
inter layers of hydrotalcite clay and studied its catalytic application
in the asymmetric Michael addition reaction.
LDHs has an anion-exchange capability and is represented by
the formula [M1−x 2+ Mx 3+ (OH)2 ](An− )x/n ·mH2 O, where M2+ could be
Mg2+ , Ni2+ , Zn2+ , etc.; M3+ could be Al3+ , Fe3+ , etc.; An− represents
interlayer anions, such as NO3 − , SO4 2− , and CO3 2− , and x typically
ranges from 0.20 to 0.33 [20]. Since the interlayer anions are easily
exchangeable, the anions in the interlayer can be exchanged by
other anions so that it make LDHs useful for many applications,
such as the sorption of many hazardous inorganic and organic ions
from aqueous solution.
Recently, some authors successfully removed metal cations
from aqueous solutions by LDHs intercalated with ethylene
diamine tetraacetic acid (EDTA) [21,22] and nitrilotriacetate (NTA)
[23].
In this paper, we prepared magnetic Mg–Al LDH intercalated
with citrate using a ion-exchange technique (labeled as magnetic
citrate·Mg–Al LDH). Citric acid exists abundantly in nature, and
it is found to be effective for the leaching of heavy metals due
to the formation of citrate–metal complexes between metals and
acids [24]. This work aims at preparing an adsorbent to effectively
remove uranium(VI) from aqueous solutions. The effects of differ-
ent parameters on uranium(VI) adsorption, such as solution pH
value, adsorbent dose, contact time and the temperature have been
studied. The adsorption kinetics, isotherms, and thermodynamics
have also been investigated.
2. Experimental
2.1. Preparation of samples
The magnetic particles were prepared according to the pre-
vious report [25]. 5.20 g of FeCl3 ·6H2 O, 2.7969 g of FeSO4 ·7H2 O
and 0.85 mL of concentrated HCl were dissolved in 200 mL of
deoxygenated water. Subsequently, the solution was slowly added
dropwise into the previously prepared 250 mL of NaOH solu-
tion (0.75 mol L−1 ). Throughout the reaction process, the solution
was stirred vigorously at 85 ◦ C under N2 protection. The reac-
tion continued for another 25 min, and the mixture was cooled to
room temperature. The black solid was washed several times with
ethanol and dried in vacuum at 60 ◦ C for 12 h.
Magnetic Mg–Al LDH was synthesized by a modified copre-
cipitation method as described elsewhere [26,27]. 0.10 mol L−1
Mg(NO3 )2 and 0.05 mol L−1 Al(NO3 )3 were dissolved in deionized
water to prepare a mixed solution. Then, 0.4 g Fe3 O4 was introduced
in this mixed solution and followed by ultrasonic for 10 min. The
solution pH was adjusted to 10.5 by addition of 0.5 mol L−1 NaOH
and 0.015 mol L−1 Na2 CO3 mixed solution. After the addition of the
solution, the mixed solution was kept stirring at 30 ◦ C for 1 h at a
constant pH of 10.5. The magnetic Mg–Al LDH was recovered by fil-
tering the resultant suspension and washed with deionized water,
and then dried in a vacuum oven at 50 ◦ C for 36 h.
622
(a)
10 20 30 40 50 60 70 80
2 degree
Fig. 1. XRD patterns of magnetic Mg–Al LDH (a) and magnetic citrate·Mg–Al LDH
(b).
2.2 g citric acid added to a suspension of magnetic Mg–Al LDH
(1.2 g) in 25 mL distilled water at 50 ◦ C. This solution was added
dropwise to 25 mL (1 mol L−1 ) NaOH solution, followed by refluxing
for 3 h. The magnetic citrate·Mg–Al LDH was recovered by filtration,
washed, and dried at 70 ◦ C for 16 h.
2.2. Adsorption experiments
The adsorption of uranium(VI) from the dilute aqueous solu-
tion was operated as the following procedure: 0.05 g magnetic
citrate·Mg–Al LDH was added to 50 mL of UO2 (NO3 )2 ·6H2 O solu-
tion. This mixture was shaken on a constant temperature oscillator
at 120 strokes min−1 . The solution pH was adjusted with 0.5 mol L−1
HNO3 or NaOH solution. At the end of the adsorption period, the
solution was separated from the solids by magnetic separation.
Then the initial and the equilibrium concentration of tested ion in
supernatant were determined. The adsorption capacity Qe (mg g−1 )
was calculated according to Eq. (1):
(C0 − Ce )V
Qe = (1)
m
where C0 (mg L−1 ) is the uranium(VI) ion concentration in the
initial solution, Ce (mg L−1 ) is the equilibrium concentration of ura-
nium(VI) ion in the supernatant, V (L) is the volume of the testing
solution and m is the weight of sorbent (g).
2.3. Characterization
X-ray diffraction (XRD) analysis was performed on a Rigaku
D/max-IIIB diffractometer with Cu K␣ irradiation ( = 1.54178 Å).
The X-ray source was operated at 40 kV and 150 mA. Fourier-
transform infrared (FT-IR) spectrum was recorded with an AVATAR
360 FT-IR spectrophotometer using a standard KBr pellets. Effluent
was analyzed using a Trace Uranium Analyzer.
3. Results and discussions
3.1. Characterization of samples
XRD patterns of magnetic Mg–Al LDH and magnetic
citrate·Mg–Al LDH are shown in Fig. 1. From the XRD pattern
of the magnetic Mg–Al LDH, except the diffraction peaks of the
LDH, the peaks marked with  of (1 1 1), (2 2 0), (3 1 1), (4 0 0),
(4 2 2), (5 1 1), (4 4 0), and (6 2 2) planes can be indexed to cubic
Fe3 O4 (JCPDS: 65-3107). Comparison of the XRD patterns finds that
222 X. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 220–227

100 200 b b
b
b a
a a
80 160 a
2895
Transmittance

Qe (mg/g)
60 120

40
80
3462 1579 623
20
1392
40
0
0
4000 3500 3000 2500 2000 1500 1000 500 25oC 35oC 45oC 55oC
wavenumber (cm-1) Temperature

Fig. 2. FT-IR spectra of magnetic citrate·Mg–Al LDH. Fig. 4. Adsorption capacity of uranium by magnetic Mg–Al LDH (a) and magnetic
citrate·Mg–Al LDH (b). Initial uranium concentration 200 mg L−1 ; pH 6.0; tempera-
ture 25–55 ◦ C; amount of adsorbent 0.05 g.

the XRD peaks for (b) are weakened and broadened at 2 values
compared to those for (a). However, the 2 values corresponding
to all of the XRD peaks for (b) are close to those for (a), suggesting
that the magnetic citrate·Mg–Al LDH has the hydrotalcite lattice
structure. For magnetic Mg–Al LDH, the observed basal spacing,
d0 0 3 , is 7.7 Å. For magnetic citrate·Mg–Al LDH, intercalation of
the chelating agents in CO3 ·Mg–Al LDH increased d0 0 3 from 7.7 Å
to 11.6 Å, the broadened XRD peaks corresponding to the basal
spacing are located at lower 2 values than those of CO3 ·Mg–Al
LDH, also indicative of a larger interlayer spacing. These results
suggest that citrate, which is larger than CO3 2− , was intercalated
into the interlayer of the Mg–Al LDH.
Fig. 2 gives the FT-IR spectra of magnetic citrate·Mg–Al LDH.
The peaks at 623 cm−1 is assigned to Fe O bond vibration of
Fe3 O4 . The intense and broad peak at 3462 cm−1 is ascribed to
the stretching vibration of hydroxyl groups of LDH layers and
interlayer water molecules. The absorption bands at 1392 and
1579 cm−1 are assigned to the characteristic symmetric and
asymmetric stretching vibrations of COO− , respectively [27]. In
addition, the characteristic peak at 2895 cm−1 , attributes to the
C H stretching vibrations. These results show that the citrate is
present in the magnetic citrate·Mg–Al LDH.
The magnetic citrate·Mg–Al LDH was dispersed in water by vig-
orous shaking, resulting in a brown suspension (Fig. 3A), and it
could be easily removed from the aqueous solution with an addition
of a permanent magnet, indicating the sensitive magnetic response
(Fig. 3B). It can provide an easy and efficient way of separating the
adsorbent from a suspension system during the sorption experi-
ments.
3.2. Uranium(VI)-sorption experiments
By using the magnetic Mg–Al LDH and the magnetic
citrate·Mg–Al LDH, the adsorption experiments were carried out for
uranium(VI) at 25, 35, 45 and 55 ◦ C, respectively. As shown in Fig. 4,
it can be seen that the adsorption ability of magnetic citrate·Mg–Al
LDH particles for uranium(VI) ions is higher than magnetic Mg–Al
LDH. By comparing the results for magnetic citrate·Mg–Al LDH with
those for magnetic Mg–Al LDH, we can attribute the increasing
capacity of uranium(VI) by the magnetic citrate·Mg–Al LDH to the

Fig. 3. Digital photograph of the aqueous solution (A) with dispersed magnetic magnetic citrate·Mg–Al LDH composite particles and (B) after magnetic separation using an
external magnetic field.
 X. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 220–227 223

200 190

180 180

160 170

Qe (mg/g)
Qe (mg/g)

140 160

120 150

100 140

80 130
2 4 6 8 10 12 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16
pH Mass of sorbent (g)
Fig. 5. Effect of pH value on adsorption property of magnetic citrate·Mg–Al LDH. Fig. 6. The effect of adsorbent dose on the uptake of uranium(VI) by magnetic
Initial uranium concentration 200 mg L−1 ; pH 2.0–12.0; temperature 25 ◦ C; amount citrate·Mg–Al LDH. Initial uranium concentration 200 mg L−1 ; pH 6.0; temperature
of magnetic citrate·Mg–Al LDH 0.05 g. 25 ◦ C; amount of magnetic citrate·Mg–Al LDH 0.005–0.15 g.

formation of a citrate–metal complexes between uranium(VI) and It can provide more sorption sites to adsorb uranium(VI) ions and
the intercalated citrate. thereby result in the increasing of uranium(VI) ion sorption. From
We have investigated the parameters which affect the ura- the economical point of view, 0.05 g adsorbent dose is selected as
nium(VI) adsorption properties of magnetic citrate·Mg–Al LDH. optimum parameter.

3.2.1. Effect of solution pH

3.2.3. Effect of contact time and adsorption dynamics
The solution pH is one of the most important parameters
Fig. 7 shows the effect of the contact time on uranium(VI)
affecting the adsorption process. In this study, the adsorption
adsorption onto magnetic citrate·Mg–Al LDH composite. The
experiments have been conducted in the initial pH range of
adsorption amount is observed to increase rapidly during start-
2.0–12.0, and the results are shown in Fig. 5. It can be seen from
ing stage of adsorption, then followed by a slowly increase rate
Fig. 5 that the uranium(VI) adsorption capacity increases steeply
and tended to equilibrium at 4 h. The fast uranium(VI) removal
with the increase of pH value, and reaches a maximum when the
rate in the beginning is attributed to the rapid diffusion of ura-
pH value is 6.0. Then, the adsorption capacity turns to decline with
nium(VI) from the solution to the external surfaces of magnetic
the increased pH value beyond 6.0. It may be attributed to the
citrate·Mg–Al LDH. In the slow adsorption process, uranium(VI)
surface charge of magnetic citrate·Mg–Al LDH which could be mod-
ions are presumably adsorbed by chelation with the ligands in the
ified by changing the pH of the solution. At low pH, uncomplexed
interlayer or the ion-exchange in the inner surface of magnetic
UO2 2+ is dominant and the binding sites of magnetic citrate·Mg–Al
citrate·Mg–Al LDH [29]. Moreover, the initial rapid adsorption may
LDH may become positively charged due to the protonation reac-
be because of a large number of available sites at the initial stage.
tion, displaying the cationic character and leading to the low
The more targets of uranium(VI) can provide higher driving force to
adsorption ability of magnetic citrate·Mg–Al LDH for uranium(VI).
facilitate the ions diffusion from the solution to active sites assem-
As pH increases, the functional groups of magnetic citrate·Mg–Al
bly [30,31]. As time proceeds, the concentration gradients became
LDH are progressively deprotonated, forming negative charge. The
reduced owing to the accumulation of uranium(VI) adsorbed on the
attractive forces between the anionic surface sites and cationic
surface sites, leading to the decrease in adsorption rate at the later
uranyl ions easily result in the formation of metal–ligand mag-
stages. Here, to further study the adsorption process, the adsorption
netic composite complexes. However, with further increase of the
pH value, the adsorption capacity decreases. It can be explained
that with the increasing of the concentration of hydroxyl, dis-
180
solved carbonate and bicarbonate anions, uranium(VI) occurs in
the solution in the form of hydroxyl and carbonate-complex ions
175
(UO2 (CO3 )3 4− , (UO2 )2 CO3 (OH)3 − , UO2 (OH)3 − etc.) that are highly
negative charged, leading to low adsorption capacity [28]. On basis 170
Qe (mg/g)

of above results, the optimum pH value is to be 6.0.

165
3.2.2. Effect of adsorbent dose
The effect of the adsorbent dose on the adsorption of uranium 160
was studied. The volume of solution (50 mL) and the concen-
tration of uranium (200 mg L−1 ) were kept constant while the 155
amount of magnetic citrate·Mg–Al LDH varied from 0.005 to 1.5 g.
150
It can be seen from Fig. 6 that the adsorption capacity of ura-
nium(VI) increases rapidly with the increase in adsorbent dose 0 100 200 300 400 500
at m < 0.05 g, and then increases unobviously at m > 0.05 g. The
increase in adsorption with an increase in amount of adsorbent can
Time (min)
be attributed to increased surface area and the availability of more
Fig. 7. Effect of contact time on uranium(VI) adsorption. Initial uranium concentra-
adsorption sites. With increasing magnetic citrate·Mg–Al LDH con- tion 200 mg L−1 ; pH 6.0; temperature 25 ◦ C; amount of magnetic citrate·Mg–Al LDH
tent, the available sites on magnetic citrate·Mg–Al LDH increase. 0.05 g.
224 X. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 220–227

Table 1
Pseudo-first and pseudo-second-order constants and values of R2 for magnetic citrate·Mg–Al LDH.
exp
Kinetic model T (◦ C) C0 (mg L−1 ) Qe (mg g−1 ) Qecal (mg g−1 ) k1ads (min−1 )/k2ads (mg−1 min−1 ) R2
−2
Pseudo-first order 25 200 180.00 23.05 2.23 × 10 0.94488
Pseudo-second order 25 200 180.00 180.50 3.02 × 10−3 0.99998

data were treated according to kinetic models of pseudo-first-order

and pseudo-second-order [32,33]. The pseudo-first-order kinetic 200
equation is given as:
dQe 160
= k1ads (Qe − Qt ) (2)
dt

Qe (mg/g)
Integrating Eq. (2) and applying the initial conditions, we have 120
25oC
ln(Qe − Qt ) = ln(Qe ) − k1ads t (3) 35oC
80
where k1ads is the rate constant of pseudo-first-order adsorption, Qe 45oC
and Qt (mg g−1 ) refer to the amount of uranium(VI) ions adsorbed
40 55oC
at equilibrium and at time (t), respectively.
The pseudo-second order model considers the rate-limiting step
as the formation chemisorptive bond involving sharing or exchange 0
of electrons between adsorbate and the adsorbent. The model can 0 20 40 60 80
be represented by the following equation: Ce (mg/L)
dQt
= k2ads (Qe − Qt )2 (4) Fig. 9. Adsorption isotherm of magnetic citrate·Mg–Al LDH for uranium(VI)
dt at different temperatures. pH 6.0; temperature 25–55 ◦ C; amount of magnetic
citrate·Mg–Al LDH 0.05 g.
Integrating Eq. (4) and applying the initial conditions, we have
t 1 t
= + (5)
Qt k2ads Qe 2 Qe
where k2ads is the rate constant of pseudo-second-order adsorption.
The values of Qe , k1ads and k2ads are calculated from the intercept
1.5 A and slope values of the plot (Fig. 8A and B) corresponding to Eqs. (3)
and (5), which are given in Table 1. The comparison between the
1.0 experimental adsorption capacity (Qexp ) values and the calculated
adsorption capacity (Qcal ) values shows that pseudo-second-order
adsorption kinetic is very close to the experimental data. More-
ln (Qe-Qt)

0.5
over, the correlation coefficient value for pseudo-second-order
model is much higher than that of pseudo first-order model, sug-
0.0
gesting that the adsorbent systems can be well-described by the
pseudo-second-order kinetic model. As the pseudo-second-order
-0.5 y=-0.00967x+1.36276 model is based on the assumption that chemical sorption is the
2
R =0.94488 rate-determining step [34], the above results obtained consistently
-1.0 suggest that the rate-determining step may be chemical adsorp-
tion and the adsorption behavior may involve the valency forces
0 50 100 150 200 250 through sharing electrons between the uranium(VI) ions and adsor-
t (h) bents [35–37].
3.0
B
2.5
3.4
2.0
t/Qt (hg/mg)

3.2 y=-3408.78764x+13.66084
2
R =0.98523
1.5
3.0

1.0 2.8
ln KD

0.5 y=0.00554x+0.01018 2.6

2
R =0.99998
0.0 2.4

0 100 200 300 400 500 2.2

t (h) 3.0x10
-3
3.1x10
-3 -3
3.2x10 3.3x10
-3
3.4x10
-3

Fig. 8. Pseudo-first-order (A), pseudo-second-order (B) plot for the removal of ura- 1/T (1/K)
nium(VI) by magnetic citrate·Mg–Al LDH. pH 6.0; temperature 25 ◦ C; amount of
magnetic citrate·Mg–Al LDH 0.05 g. Fig. 10. Relationship curve between ln KD and 1/T.
 X. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 220–227 225

0.20
A
0.18

Ce/Qe (g/L)
0.16

0.14

y=-0.00474x+0.20254
0.12
2
R =0.88275

0.10
2 4 6 8 10 12 14 16 18 20 22

Ce (mg/L)
5.5
B
y=1.32936x+1.17667
5.0
2
R =0.99737
4.5
lnQe

4.0

3.5

3.0

1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2

lnCe
Fig. 11. Langmuir (A) and Freundlich (B) plot for the removal of uranium(VI) by magnetic citrate·Mg–Al LDH. pH 6.0; temperature 25 ◦ C; amount of magnetic citrate·Mg–Al
LDH 0.05 g.

3.2.4. Effect of temperature and adsorption thermodynamics where KD is the distribution coefficient (mL g−1 ), H◦ is standard
To investigate the thermodynamics of adsorption, temperature enthalpy(kJ mol−1 ), S◦ is standard entropy (J mol−1 K−1 ), T is the
experiments were carried out at 25, 35, 45 and 55 ◦ C at pH 6.0 absolute temperature (K), R is the gas constant (8.314 J mol−1 K−1 )
(Fig. 9). It can be observed that the adsorption capacity of ura- and G◦ is the standard Gibbs free energy. The values of H◦ and
nium(VI) ion increases with increasing temperature, indicating that S◦ are calculated from the slope and intercept of the linear regres-
the process is endothermic in nature. The Gibbs energy (G◦ ), sion of ln KD versus 1/T (Fig. 10). The data of G◦ , H◦ and S◦ are
enthalpy (H◦ ), and entropy (S◦ ) are calculated from the follow- together summarized in Table 2.
ing equation: The positive value of H◦ indicates the endothermic nature
o o of the adsorption of uranium(VI) on magnetic citrate·Mg–Al LDH.
H S Hence, the uranium(VI) ions uptake increases with the increase
ln KD = − + (6)
RT R in temperature. The positive value of S◦ suggests the increased
o
G = H − TS
o o
(7) randomness at the solid/liquid interface during the adsorption of

Table 2
Thermodynamics parameters for uranium adsorption on magnetic citrate·Mg–Al LDH.

C0 (mg L−1 ) H◦ (kJ mol−1 ) S◦ (J mol−1 K−1 ) G◦ (kJ mol−1 )

25 ◦ C 35 ◦ C 45 ◦ C 55 ◦ C

200 28.3407 113.5762 −5.5220 −6.6578 −7.8333 −8.9293

226 X. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 414 (2012) 220–227
Table 3
Isotherm constants and values of R2 for magnetic citrate·Mg–Al LDH.
Parameter Value
Langmuir isotherm Qm (mg g ) −1
210.97
b (L mg−1 ) 0.0234
Freundlich isotherm K (L g−1 ) 3.2436
n 0.7522
uranium(VI) on magnetic citrate·Mg–Al LDH. The Gibbs free energy
is found to be decreasing with rise in temperature, which indicates
the feasibility and spontaneity of the adsorption process.
3.2.5. Adsorption isotherms of uranium
The equilibrium data were analyzed using the Langmuir and
Freundlich equilibrium models in order to obtain the best fitting
isotherm. The Langmuir equation has been used extensively for
dilute solutions in the following form [38,39]
Ce 1 Ce
= +
Qe bQm Qm
where Ce (mg L−1 ) is the equilibrium concentration of uranium(VI)
ions, Qe (mg g−1 ) is the adsorbed value of uranium(VI) ions at equi-
librium concentration, Qm (mg g−1 ) is the saturated adsorption
amount of uranium(VI), b is Langmuir constant. According to Eq.
(8), a line is obtained and it is presented in Fig. 11A. The values of
Qm and b can be obtained by the slope and intercept of the line and
given in Table 3.
The essential features of the Langmuir isotherm model can be
expressed in terms of a dimensionless constant separation factor
or equilibrium parameter RL [40], which is defined by
1
RL =
1 + bC0
where C0 is the initial metal ion concentration. The value of sepa-
ration factor constant (RL ) that gives indication for the possibility
of the adsorption process to proceed: RL > 1, unfavorable; RL = 1,
favorable (linear); 0 < RL < 1, favorable; RL = 0, irreversible; RL < 0,
unfavorable.
In this study RL value as 0.1761 indicates that magnetic
citrate·Mg–Al LDH is a suitable adsorbent for adsorption of ura-
nium(VI) from aqueous solutions.
The results of uranium(VI) adsorption onto magnetic
citrate·Mg–Al LDH have also been analyzed by using the Freund-
lich model to evaluate parameters associated with adsorption
behavior. The Freundlich equation is [41]
1/n
Qe = KCe
Eq. (10) can be rearranged to linear from
1
ln Qe = ln K + ln Ce
n [7] Y.J. Jung, S. Kim, S. Park, J.M. Kim, Application of polymer-modified nanoporous
where K and n are the Freundlich constants, which represent sorp-
tion capacity and sorption intensity, respectively. They can be
evaluated from the intercept and slope of the linear plot of ln Qe
versus ln Ce (Fig. 11B).
The adsorption constants of uranium(VI) ions onto magnetic
citrate·Mg–Al LDH are calculated according to Langmuir and
Freundlich adsorption models and the results are listed in Table 3.
Based on correlation coefficient values (>0.99), it is found that the
adsorption onto magnetic citrate·Mg–Al LDH can be best described
by the Freundlich model.
4. Conclusions
Magnetic citrate·Mg–Al LDH, which had C6 H5 O7 3− intercalated
in the interlayer, was prepared via ion-exchange technique. Some
citrate acid anions were likely adsorbed onto the surfaces as well.
The magnetic citrate·Mg–Al LDH is superior to the magnetic Mg–Al
R2 LDH in the uptake of uranium(VI) from solution at a constant
0.88275 pH of 6.0. This is mainly attributable to the formation of chelate
complex between uranium(VI) and the intercalated or adsorbed
0.99737 C6 H5 O7 3− . Thus, the citrate in the magnetic Mg–Al LDH has contri-
bution to the uranium(VI) uptake from solution. The as-prepared
magnetic citrate·Mg–Al LDH composite shows an excellent abil-
ity to remove uranium from aqueous solution and the maximum
uranium(VI) sorption capacity is about 180.00 mg g−1 at 25 ◦ C. In
addition, the magnetic citrate·Mg–Al LDH is easily separated by
the external magnetic field; by this way, the problem of phase
separation using the traditional adsorbents can be resolved. The
equilibrium isotherm data are fitted well by Freundlich model and
pseudo-second-order equation. The thermodynamic parameters
G◦ , H◦ and S◦ values of uranium(VI) adsorption onto magnetic
citrate·Mg–Al LDH show the process is endothermic and sponta-
neous in nature. The results of the present investigation illustrate
that magnetic citrate·Mg–Al LDH could be a perfect candidate as an
(8)
adsorbent to remove the toxic and radioactive uranium(VI) from
solution.
Acknowledgments
This work was supported by the Fundamental Research
Funds of the Central University (HEUCFZ1107), Science and
Technology Planning Project from Education Department of Hei-
longjiang Province (11553044), High Education Doctoral Fund
(160100110010), Special Innovation Talents of Harbin Science and
Technology (2010RFXXG007), the foundation of Harbin Engineer-
(9) ing University (No. HEUFT07053).
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